Chitin and Chitosan-Structurally Related Precursors of Dissimilar Hard Carbons for Na-Ion Battery

Hard carbons (HCs) prepared from renewable precursors are promising cost-effective electrode-material candidates for the application in Na-ion battery. Usually these materials are derived from cellulose. Here, however, we demonstrate that other polysaccharides, such as chitin and chitosan, can be as well up-and-coming parent materials of HCs. Despite structural similarities, thermal decomposition of these two biopolymers proceeds differently, contributing to the discrepancies in physicochemical properties of resulting HCs. Although chitin- and chitosan-derived HCs have comparable d-spacings and crystallite sizes, solid-state pyrolysis of the former biopolymer leads to micromesoporous material with significant specific surface area, while that of chitosan yields nonporous carbon. Despite that, both materials deliver similar initial specific charge of 280 mAh g(-1) (at C/10 rate), and their electrochemical performance starts to diverge only upon longer cycling at higher rate. With time, inorganic contaminants present in chitosan-derived HC presumably delay the diffusion of Na ions to and within the electrode and slow the rate of electrochemical reactions, eventually triggering polarization buildup. Further optimization of the chitosan-derived HC through acid treatment enables unblocking some of the micropores and increasing the carbon content in this material, therefore enhancing its active surface area and suppressing continuous fading of the specific charge.